JPH0214232A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH0214232A JPH0214232A JP16271488A JP16271488A JPH0214232A JP H0214232 A JPH0214232 A JP H0214232A JP 16271488 A JP16271488 A JP 16271488A JP 16271488 A JP16271488 A JP 16271488A JP H0214232 A JPH0214232 A JP H0214232A
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- rubber
- resin
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000005060 rubber Substances 0.000 claims abstract description 14
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims abstract description 11
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 8
- 229920005989 resin Polymers 0.000 claims description 43
- 239000011347 resin Substances 0.000 claims description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229920006249 styrenic copolymer Polymers 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 11
- 229920006026 co-polymeric resin Polymers 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract 2
- 150000001408 amides Chemical class 0.000 abstract 1
- 229920001693 poly(ether-ester) Polymers 0.000 abstract 1
- -1 vinyl fatty acids Chemical class 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 2
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- HGRZLIGHKHRTRE-UHFFFAOYSA-N 1,2,3,4-tetrabromobutane Chemical compound BrCC(Br)C(Br)CBr HGRZLIGHKHRTRE-UHFFFAOYSA-N 0.000 description 1
- YAOMHRRYSRRRKP-UHFFFAOYSA-N 1,2-dichloropropyl 2,3-dichloropropyl 3,3-dichloropropyl phosphate Chemical compound ClC(Cl)CCOP(=O)(OC(Cl)C(Cl)C)OCC(Cl)CCl YAOMHRRYSRRRKP-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- MXSKJYLPNPYQHH-UHFFFAOYSA-N 2,4-dimethyl-6-(1-methylcyclohexyl)phenol Chemical compound CC1=CC(C)=C(O)C(C2(C)CCCCC2)=C1 MXSKJYLPNPYQHH-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- IZUJOTOTCFZBMQ-UHFFFAOYSA-O 2-hydroxyethyl(dimethyl)azanium;nitrate Chemical compound [O-][N+]([O-])=O.C[NH+](C)CCO IZUJOTOTCFZBMQ-UHFFFAOYSA-O 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- FAVWXKQADKRESO-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-1-ene Chemical compound CC=C.CC(=C)C(O)=O FAVWXKQADKRESO-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- BJFLSHMHTPAZHO-UHFFFAOYSA-N benzotriazole Chemical compound [CH]1C=CC=C2N=NN=C21 BJFLSHMHTPAZHO-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- LHLUQDDQLCJCFU-UHFFFAOYSA-L disodium;1-sulfocyclohexa-3,5-diene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1(C([O-])=O)CC(C([O-])=O)=CC=C1 LHLUQDDQLCJCFU-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- QVKOLZOAOSNSHQ-UHFFFAOYSA-N prop-1-ene;prop-2-enoic acid Chemical compound CC=C.OC(=O)C=C QVKOLZOAOSNSHQ-UHFFFAOYSA-N 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- HLWRUJAIJJEZDL-UHFFFAOYSA-M sodium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC([O-])=O HLWRUJAIJJEZDL-UHFFFAOYSA-M 0.000 description 1
- UCWBKJOCRGQBNW-UHFFFAOYSA-M sodium;hydroxymethanesulfinate;dihydrate Chemical compound O.O.[Na+].OCS([O-])=O UCWBKJOCRGQBNW-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- WRSPWQHUHVRNFV-UHFFFAOYSA-N tris[3,5-di(nonyl)phenyl] phosphite Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=CC(OP(OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)=C1 WRSPWQHUHVRNFV-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 a、産業上の利用分野 本発明は新規な熱可塑性樹脂組成物に関する。[Detailed description of the invention] a. Industrial application field The present invention relates to a novel thermoplastic resin composition.
さらに詳しくは、持続性のある帯電防止効果を有し且つ
耐衝撃性、成形外観、ウェルド強度、成形加工性の優れ
た熱可塑性樹脂組成物に関する。More specifically, the present invention relates to a thermoplastic resin composition that has a long-lasting antistatic effect and has excellent impact resistance, molded appearance, weld strength, and molding processability.
b、従来の技術
合成高分子材料(以下、樹脂という)を電気、電子機器
部品用として使用する場合、その帯電防止効果が問題と
なる。すなわち、これら樹脂成形品に電荷が帯電すると
、その電荷によって電気、電子機能の性能が悪影響を受
けるからである。またほこりの付着により商品価値が著
しく低下する場合がある。これらの問題点を改良するた
め、帯電防止剤の練り込み、あるいは塗布がおこなわれ
ている。それによれば、−時的には効果を発運するが、
長時間にわたって効果が持続しないという欠点がある。b. Prior Art When synthetic polymer materials (hereinafter referred to as resins) are used for electrical and electronic equipment parts, their antistatic effect becomes a problem. That is, when these resin molded products are charged with electric charge, the performance of electrical and electronic functions is adversely affected by the electric charge. Further, the commercial value may be significantly reduced due to the adhesion of dust. In order to improve these problems, antistatic agents are mixed in or coated. According to this, - although it has a temporal effect,
The drawback is that the effect does not last for a long time.
特開昭60−23435号公報には、
(AI) ポリエーテルエステルアミド 5〜80重
量%と
(Bl) カルボキシル基を含有する変性ビニル系重
合体95〜20重量%
と混合してなる制電性樹脂組成物が開示されている。同
公開公報の実施例2には、上記(AI)および(Bl)
成分にさらにABS樹脂(重合体C=4)を25重量%
および30重量%で含有する樹脂組成物が開示され、そ
れらの樹脂組成物のアイゾツト衝撃強度(ノツチ付)が
10〜12kgc m / c mであることが記載さ
れている。JP-A No. 60-23435 discloses an antistatic property obtained by mixing (AI) 5 to 80% by weight of polyether ester amide and (Bl) 95 to 20% by weight of a modified vinyl polymer containing a carboxyl group. A resin composition is disclosed. Example 2 of the same publication includes the above (AI) and (Bl).
In addition, 25% by weight of ABS resin (polymer C = 4)
and 30% by weight, and the Izot impact strength (notched) of these resin compositions is described to be 10 to 12 kgcm/cm.
特開昭62−241945号公報には、(A2) ポリ
エーテルエステルアミド 1〜40重量部、
(B2) ABS系グラグラフト共重合体5〜98重
量部
および
(C2) カルボキシル基を含有する変性ビニル系重合
体 0.1〜20重量部
からなる熱可塑性樹脂組成物が開示されている。JP-A-62-241945 discloses (A2) 1 to 40 parts by weight of polyether ester amide, (B2) 5 to 98 parts by weight of ABS-based graph graft copolymer, and (C2) modified vinyl-based material containing a carboxyl group. A thermoplastic resin composition comprising 0.1 to 20 parts by weight of a polymer is disclosed.
上記公開公報には、該熱可塑性樹脂組成物は成形加工性
に優れ、層状剥離のなく表面外観が優れていることが開
示されている。The above-mentioned publication discloses that the thermoplastic resin composition has excellent moldability, no delamination, and an excellent surface appearance.
特開昭62−241945号公報には、特開昭60−2
3435号の組成物の欠点としてカルボキシル基含有変
性ビニル系重合体の配合量が多いため、成形加工性が低
く物性の再現性が悪いことが述べられている。本発明者
らの実験においても、アイゾツト衝撃強度、流動性、成
形外観等が悪いことが明らかになった。JP-A No. 62-241945 includes JP-A No. 60-2
It is stated that the disadvantages of the composition of No. 3435 are that the compounded amount of the carboxyl group-containing modified vinyl polymer is high, resulting in poor moldability and poor reproducibility of physical properties. Experiments conducted by the present inventors also revealed that the Izot impact strength, fluidity, molded appearance, etc. were poor.
これはカルボキシル基含有変性ビニル系重合体の配合量
が多いだけでなく、第3成分のABS樹脂量が少ないこ
とが関係していると教えられる。It is believed that this is related not only to the large amount of the carboxyl group-containing modified vinyl polymer blended, but also to the small amount of the ABS resin as the third component.
これらの欠点は、特開昭62−241945号公報にお
いて、カルボキシル基含有変性ビニル系重合体量の減量
と、第3成分であるABS樹脂の増量によりかなり改良
されている。These drawbacks are considerably improved in JP-A-62-241945 by reducing the amount of the carboxyl group-containing modified vinyl polymer and increasing the amount of the third component, ABS resin.
しかし、カルボキシル基含有変性ビニル系重合体の減量
のためウェルド強度が低下する欠点が見られる。However, there is a drawback that the weld strength decreases due to the weight loss of the carboxyl group-containing modified vinyl polymer.
C0発明が解決しようとする問題点
本発明の目的は、帯電防止効果を有する新規な熱可塑性
樹脂組成物を提供することにある。Problems to be Solved by the C0 Invention An object of the present invention is to provide a novel thermoplastic resin composition having an antistatic effect.
本発明の他の目的は、帯電防止効果を有し、成形加工性
および成形外観に優れているとともに、さらに耐衝撃性
およびウェルド強度がバランスよく優れた熱可塑性樹脂
組成物を提供することにある。Another object of the present invention is to provide a thermoplastic resin composition that has an antistatic effect, is excellent in molding processability and molded appearance, and also has excellent impact resistance and weld strength in a well-balanced manner. .
本発明のさらに他の目的は、従来技術で達成されなかっ
た優れた耐衝撃性とウェルド強度を兼備した帯電防止効
果を有する熱可塑性樹脂組成物を提供することにある。Yet another object of the present invention is to provide a thermoplastic resin composition that has both excellent impact resistance and weld strength, and has an antistatic effect that has not been achieved by the prior art.
本発明のさらに他の目的および利点は以下の説明から明
らかとなろう。Further objects and advantages of the present invention will become apparent from the description below.
d1問題を解決するための手段および作用本発明によれ
ば、本発明のかかる目的および利点は、
(A) カルボキシル基含有不飽和化合物を共重合成
分として含有するゴム強化スチレン系共重合体樹脂、
(B) カルボキシル基含有不飽和化合物を共重合成
分として含有しないゴム強化もしくは非強化スチレン系
共重合体樹脂および
(C) ポリエーテルアミドおよびポリエーテルエス
テルアミドの少くともいずれか一方を含有して成り、そ
して
(D) 上記(A)、(B)および(C)成分の合計
量を基準として、(A)成分は22〜45重量%の範囲
にあり、(B)成分は50〜77重量%の範囲にありそ
して(C)成分は1〜26重量%の範囲にあり、
(E) 上記(A)成分樹脂中の該カルボキシル基含
有化合物の含有量は(A)成分に基づき0゜1−10重
量%の範囲にあり且つ(A)、(B)および(C)成分
の合計量に基づき0.02〜4重量%の範囲にあり、
(F) 上記(A)成分樹脂中のゴム成分又は上記(
B)成分樹脂がゴム成分を含有する場合には(A)成分
樹脂と(B)成分樹脂中のゴム成分について、平均グラ
フト率が少くとも20重量%であり且つアセトン可溶分
の極限粘度(30℃、メチルエチルケトン中)が少くと
も0.35dff/gであり、そして
(G) 上記(A)、(B)および(C)成分の合計
量を基準としてゴム成分の含有量が5〜40重量%の範
囲にある、
ことを特徴とする熱可塑性樹脂組成物によって達成され
る。Means and operation for solving the d1 problem According to the present invention, the objects and advantages of the present invention are as follows: (A) a rubber-reinforced styrenic copolymer resin containing a carboxyl group-containing unsaturated compound as a copolymerization component; (B) A rubber-reinforced or non-reinforced styrenic copolymer resin that does not contain a carboxyl group-containing unsaturated compound as a copolymerization component, and (C) a resin that contains at least one of polyetheramide and polyetheresteramide. , and (D) based on the total amount of components (A), (B), and (C) above, component (A) is in the range of 22 to 45% by weight, and component (B) is in the range of 50 to 77% by weight. and (C) component is in the range of 1 to 26% by weight, and (E) the content of the carboxyl group-containing compound in the (A) component resin is 0°1- based on component (A). in the range of 10% by weight and in the range of 0.02 to 4% by weight based on the total amount of components (A), (B) and (C), (F) the rubber component in the resin component (A) Or above (
When the component resin B) contains a rubber component, the average grafting rate of the rubber components in the component resins (A) and (B) is at least 20% by weight, and the intrinsic viscosity of the acetone soluble portion ( (30°C, in methyl ethyl ketone) is at least 0.35 dff/g, and (G) the content of the rubber component is 5 to 40% by weight based on the total amount of components (A), (B) and (C) above. % of the thermoplastic resin composition.
本発明の熱可塑性樹脂組成物(以下、本発明の組成物と
いうことがある)は、上記のとおり、(A)、(B)お
よび(C)の3成分を必須成分として含有11、しかも
上記(D)〜(G)に記載されているように、重合体組
成が厳格に特定されている点で特徴的である。As described above, the thermoplastic resin composition of the present invention (hereinafter sometimes referred to as the composition of the present invention) contains the three components (A), (B), and (C) as essential components. As described in (D) to (G), it is characteristic in that the polymer composition is strictly specified.
(A)成分のカルボキシル基含有不飽和化合物を共重合
成分として含有するゴム強化スチレン系共重合体樹脂(
以下(A)成分樹脂ということがある)は、共重合成分
として含有する該カルボキシル基含有化合物を、例えば
、(1)ゴム強化スチレン系共重合体のゴム質重合体の
構成成分として、(2)ゴム強化スチレン系共重合体の
ゴム質重合体へのグラフト成分として、あるいは(3)
ゴム強化スチレン系共重合体のマトリックス重合体部分
の構成成分として、含有するいずれの樹脂であることも
できる。Rubber-reinforced styrenic copolymer resin containing the carboxyl group-containing unsaturated compound of component (A) as a copolymerization component (
(hereinafter sometimes referred to as (A) component resin), the carboxyl group-containing compound contained as a copolymerization component is used as a constituent component of the rubbery polymer of (1) rubber-reinforced styrenic copolymer (2). ) as a graft component of a rubber-reinforced styrenic copolymer to a rubbery polymer, or (3)
It can be any resin contained as a component of the matrix polymer portion of the rubber-reinforced styrenic copolymer.
これらのうち、共重合成分として含有する該カルボキシ
ル基含有化合物を上記(1)又は(2)の態様で含有す
る樹脂は、本発明の組成物に特に高い耐衝撃強度とウェ
ルド強度を与えしかも良好な成形外観を付与するので、
好ましい。Among these, the resin containing the carboxyl group-containing compound as a copolymerization component in the embodiment (1) or (2) above gives the composition of the present invention particularly high impact strength and weld strength, and has good properties. Because it gives a molded appearance,
preferable.
ゴム質重合体としては、例えばエチレン−プロピレンの
ランダム共重合体およびブロック共重合体、エチレン−
ブテンのランダム共重合体およびブロック共重合体など
のエチレンとa−オレフィンとの共重合体;エチレン−
メタクリレート、エチレン−ブチルアクリレートなどの
エチレンと不飽和カルボン酸エステルとの共重合体:エ
チレンー酢酸ビニルなどのエチレンと脂肪酸ビニルとの
共重合体;エチレンープロピレンーエチリデンノルホル
ネン共重合体、エチレン−プロピレン−ヘキサジエン共
重合体などのエチレン−プロピレン−非共役ジェンター
ポリマー:ポリブタジェン、イソプレン、スチレン−ブ
タジェンのランダム共重合体およびブロック共重合体;
更に該ブロック共重合体の水添物;アクリロニトリル−
ブタジェン共重合体、ブタジェン−イソプレン共重合体
などのジエン系ゴム;ブチレン−イソグレン共重合体な
どを挙げることができる。Examples of rubbery polymers include ethylene-propylene random copolymers and block copolymers, and ethylene-propylene random copolymers and block copolymers.
Copolymers of ethylene and a-olefins, such as random and block copolymers of butene;
Copolymers of ethylene and unsaturated carboxylic acid esters such as methacrylate and ethylene-butyl acrylate; Copolymers of ethylene and vinyl fatty acids such as ethylene-vinyl acetate; ethylene-propylene-ethylidene norhorne copolymers, ethylene- Ethylene-propylene-nonconjugated genterpolymers such as propylene-hexadiene copolymers: random and block copolymers of polybutadiene, isoprene, styrene-butadiene;
Furthermore, a hydrogenated product of the block copolymer; acrylonitrile-
Examples include diene rubbers such as butadiene copolymers and butadiene-isoprene copolymers; butylene-isogrene copolymers.
これらのゴム質重合体は一種又は二種以上併用すること
ができる。These rubbery polymers can be used alone or in combination of two or more.
これらのうち、耐衝撃性などの点で好ましいゴム質重合
体はジエン系ゴム、エチレン−プロピレンゴム、エチレ
ン−プロピレン−非共役ジェンターポリマーであり、さ
らに好ましくはポリブタジェンおよびスチレン含有率が
50重量%以下であるスチレン−ブタジェン共重合体で
ある。Among these, preferable rubbery polymers in terms of impact resistance and the like are diene rubber, ethylene-propylene rubber, and ethylene-propylene-nonconjugated genter polymer, and more preferably polybutadiene and styrene content of 50% by weight or less. It is a styrene-butadiene copolymer.
また、カルボキシル基含有不飽和化合物としては、例え
ばアクリル酸、メタクリル酸、クロトン酸、桂皮酸、イ
タコン酸、マレイン酸などを挙げることができる。これ
らのうち、アクリル酸およびメタクリル酸が好ましい。Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferred.
カルボキシル基含有不飽和化合物は一種又は二種以上併
用することができる。The carboxyl group-containing unsaturated compounds can be used alone or in combination of two or more.
本発明における上記ゴム強化スチレン系共重合体は、例
えばゴム質重合体の存在下に、カルボキシル基含有化合
物、スチレン系化合物および必要に応じて共重合可能な
他の単量体を重合せしめることによって製造することが
できる。The rubber-reinforced styrenic copolymer of the present invention can be produced by, for example, polymerizing a carboxyl group-containing compound, a styrene compound, and, if necessary, other copolymerizable monomers in the presence of a rubbery polymer. can be manufactured.
スチレン系化合物としては、例えばスチレン、a−メチ
ルスチレン、メチルスチレン、ビニルキシレン、モノク
ロルスチレン、ジクロルスチレン、モノブロムスチレン
、ジブロムスチレン、ptert−7’チルスチレン、
エチルスチレン、ビニルナフタレン、0−メチルスチレ
ン、p−メチルスチレン、ジメチルスチレンなどを挙げ
ることができる。Examples of styrenic compounds include styrene, a-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, ptert-7'tylstyrene,
Examples include ethylstyrene, vinylnaphthalene, 0-methylstyrene, p-methylstyrene, and dimethylstyrene.
これらのスチレン系化合物は一種又は二種以上併用する
ことができる。スチレン系化合物としては、スチレンお
よび50重量%以上のスチレンと他のスチレン系化合物
の併用がとりわけ好ましい。These styrene compounds can be used alone or in combination of two or more. As the styrene compound, styrene and a combination of 50% by weight or more of styrene and other styrene compounds are particularly preferred.
また、必要に応じ使用することのできる共重合可能な他
の単量体としては、例えばマレイミド系化合物、ビニル
シアン化合物及びこれらと共重合可能な他のビニル単量
体を挙げることができる。Examples of other copolymerizable monomers that can be used as necessary include maleimide compounds, vinyl cyan compounds, and other vinyl monomers copolymerizable with these compounds.
マレイミド系化合物としては例えば、マレイミド、N−
メチルマレイミド、N−エチルマレイミF、N−フェニ
ルマレイミド、N−o−クロルフェニルマレイミド、N
−シクロへキシルマレイミドなどが挙げられる。特に好
ましくはN−7エ二ルマレイミl’、N−o−クロルフ
ェニルマレイミド、N−シクロへキシルマレイミドなど
である。Examples of maleimide compounds include maleimide, N-
Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide, N
-Cyclohexylmaleimide and the like. Particularly preferred are N-7 enylmaleimide, N-o-chlorophenylmaleimide, N-cyclohexylmaleimide, and the like.
これらは1種または2種以上を併用してもよい。These may be used alone or in combination of two or more.
ビニルシアン化合物としては、例えばアクリロニトリル
、メタクリロニトリルなどであり、これらのうちでは好
ましくはアクリロニトリルである。Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and among these, acrylonitrile is preferred.
他の共重合可能なビニル化合物としては、例えばメチル
アクリレート、エチルアクリレート、プロピレンアクリ
レートなどのアクリル酸のアルキルエステル;メチルメ
タアクリレート、エチルメタクリレート、プロピレンメ
タクリレート、などのメタクリル酸アルキルエステル;
無水マレイン酸、無水イタコン酸、無水シトラコン酸な
どの不飽和酸無水物が挙げられる。これらの1種でも2
種以上併用してもよい。Other copolymerizable vinyl compounds include, for example, acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, and propylene acrylate; methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and propylene methacrylate;
Examples include unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride, and citraconic anhydride. Even one of these two
More than one species may be used in combination.
本発明の組成物で用いられる上記(A)成分樹脂は、共
重合成分としてのカルボキシル基含有不飽和化合物を、
(A)成分樹脂に基づき0.1〜IO重量%の範囲の量
および(A)、(B)および(C)成分の合計量に基づ
き0.02〜4重量%の範囲の量で含有する。いずれの
範囲の下限を割る量でも得られる組成物の耐衝撃性およ
びウェルド強度保持が低くなり、他方上限を超える量で
は得られる組成物の耐衝撃性、ウェルド強度および成形
外観が悪くなる。The above (A) component resin used in the composition of the present invention contains a carboxyl group-containing unsaturated compound as a copolymerization component,
Contained in an amount ranging from 0.1 to IO weight % based on the component resin (A) and from 0.02 to 4 weight % based on the total amount of components (A), (B), and (C). . If the amount falls below the lower limit of either range, the resulting composition will have poor impact resistance and weld strength retention, while if the amount exceeds the upper limit, the resulting composition will have poor impact resistance, weld strength, and molded appearance.
本発明の組成物で、上記(A)成分樹脂は、共重合成分
としてのカルボキシル基含有不飽和化合物を、(A)成
分樹脂に基づき、好ましくは0゜2〜9重量%、より好
ましくは0.2〜8重量%で含有し、また(A)、(B
)および(C)成分の合計量に基づき、好ましくは0.
02〜3.5重量%、より好ましくは0.02〜3重量
%で含有する。In the composition of the present invention, the component resin (A) preferably contains a carboxyl group-containing unsaturated compound as a copolymerization component, based on the component resin (A), preferably 0.2 to 9% by weight, more preferably 0. .2 to 8% by weight, and (A), (B
) and (C), preferably 0.
The content is preferably 0.02 to 3.5% by weight, more preferably 0.02 to 3% by weight.
本発明の組成物の(B)成分はカルボキシル基含有化合
物を共重合成分として含有しないゴム強化もしくは非強
化のスチレン系共重合体樹脂(以下CB)成分樹脂とい
うことがある)である。Component (B) of the composition of the present invention is a rubber-reinforced or non-reinforced styrenic copolymer resin (hereinafter sometimes referred to as CB component resin) that does not contain a carboxyl group-containing compound as a copolymerization component.
(B)成分樹脂は、例えばゴム質重合体の存在下又は非
存在下に、スチレン系化合物および必要に応じ共重合可
能な他の単量体を重合せしめることによって製造するこ
とができる。The component resin (B) can be produced, for example, by polymerizing a styrene compound and, if necessary, other copolymerizable monomers in the presence or absence of a rubbery polymer.
スチレン系化合物としては、上記(A)成分樹脂につい
て記載したと同じ化合物を使用することができる。As the styrene compound, the same compounds as described for the resin component (A) above can be used.
共重合可能な他の単量体は、例えばマレイミド系化合物
、ビニルシアン化合物および共重合可能な他のビニル単
量体であり、これらの例も上記(A)成分樹脂について
記載しt;とおりである。Other copolymerizable monomers include, for example, maleimide compounds, vinyl cyanide compounds, and other copolymerizable vinyl monomers, and these examples are also as described for the component resin (A) above. be.
(B)成分樹脂としては、ゴム質重合体の存在下にスチ
レン系化合物および必要に応じ共重合可能な他の単量体
を重合せしめて得られた重合体、ゴム質重合体の非存在
下に上記七ツマ−を重合せしめて得られた重合体および
これらの重合体の混合物のいずれであることもできる。(B) The component resin is a polymer obtained by polymerizing a styrene compound and other copolymerizable monomers as necessary in the presence of a rubbery polymer, or a polymer obtained by polymerizing a styrene compound and other monomers that can be copolymerized as necessary, in the absence of a rubbery polymer. It can be either a polymer obtained by polymerizing the above-mentioned hexamer or a mixture of these polymers.
(B)成分樹脂としては、例えばアクリロニトリル−ブ
タジェンゴム−スチレン樹m(ABS樹脂)、アクリロ
ニトリル−エチレンプロピレンゴム−スチレン樹脂(A
ES樹脂)、アクリロニトリルースチレン共重合体(A
S樹脂)、メタクリル酸メチル−スチレン共重合体(M
S樹脂)、ハイインパクトポリスチレン(HIPS)、
アクリロニトリル−〇−ブチルアクリレートゴムースチ
レン樹脂(AAS樹脂)等を挙げることができる。(B) Component resins include, for example, acrylonitrile-butadiene rubber-styrene resin (ABS resin), acrylonitrile-ethylenepropylene rubber-styrene resin (A
ES resin), acrylonitrile-styrene copolymer (A
S resin), methyl methacrylate-styrene copolymer (M
S resin), high impact polystyrene (HIPS),
Examples include acrylonitrile-〇-butyl acrylate rubber-styrene resin (AAS resin).
本発明の(A)成分樹脂および(B)成分樹脂中のゴム
成分はいずれも少くとも20重量%のグラフト率と少く
とも0.35dI2/gのアセトン可溶分(メチルエチ
ルケトン溶媒、30°Cで測定)の極限粘度を有する。The rubber components in the (A) component resin and (B) component resin of the present invention both have a grafting rate of at least 20% by weight and an acetone soluble content of at least 0.35 dI2/g (methyl ethyl ketone solvent, at 30°C). It has an intrinsic viscosity of (measured).
グラフト率が20重量%未満の場合、組成物の光沢度が
成形温度の影響を受けて光沢度が低くなり、外観ムラが
発生し、成形外観が悪くなる。When the grafting rate is less than 20% by weight, the gloss of the composition is affected by the molding temperature, resulting in low gloss, uneven appearance, and poor molded appearance.
グラフト率は下記の測定法によって定義される。Grafting ratio is defined by the following measurement method.
試料1gを精秤採取し、これにアセトン20ccを加え
、10時間振盪させ、その後、回転数20゜000rp
mの遠心分離機を用いて可溶分と不溶分に分離し、不溶
分を真空乾燥機で乾燥し、不溶分(C)を得る。一方、
重合組成と重合転化率から不溶分(C)中のゴム量(R
)を算出する。Accurately weigh 1 g of sample, add 20 cc of acetone to it, shake for 10 hours, and then rotate at 20°000 rpm.
A soluble fraction and an insoluble fraction are separated using a centrifugal separator, and the insoluble fraction is dried using a vacuum dryer to obtain an insoluble fraction (C). on the other hand,
From the polymerization composition and polymerization conversion rate, the amount of rubber (R
) is calculated.
次式によりグラフト率を算出する。Calculate the grafting rate using the following formula.
ゴム成分のグラフト率は、好ましくは少くとも25重量
%であり、さらに好ましくは30〜150重量%である
。The grafting rate of the rubber component is preferably at least 25% by weight, more preferably from 30 to 150% by weight.
アセトン可溶分の極限粘度が0.35dQ/gに及ばな
い場合には、得られる組成物の耐衝撃性、ウェルド強度
が低くなる。アセトン可溶分の極限粘度は好ましくは0
.37dQ/g−1,OdQ/gである。If the intrinsic viscosity of the acetone soluble component is less than 0.35 dQ/g, the resulting composition will have low impact resistance and weld strength. The intrinsic viscosity of the acetone soluble component is preferably 0.
.. 37dQ/g-1, OdQ/g.
また、本発明の組成物の(A)、(B)および(C)成
分の合計量に基づき、ゴム成分は5〜40重量%で含有
される。Further, the rubber component is contained in an amount of 5 to 40% by weight based on the total amount of components (A), (B), and (C) of the composition of the present invention.
5重量%未満の場合は得られる組成物の耐衝撃性、ウェ
ルド強度が低く、又、40重量%を越えて得られる組成
物の成形加工性が悪くなり、成形外観も悪くなる。If it is less than 5% by weight, the resulting composition will have low impact resistance and weld strength, and if it exceeds 40% by weight, the resulting composition will have poor moldability and poor molded appearance.
ゴム成分は、同じ基準に対し、好ましくは5〜35重量
%、より好ましくは6〜30重量%で含有される。The rubber component is preferably contained in an amount of 5 to 35% by weight, more preferably 6 to 30% by weight, based on the same criteria.
本発明の組成物の(C)成分はポリエーテルアミドおよ
びポリエーテルエステルアミドの少くともいずれか一方
である。ポリエーテルアミドおよびポリエーテルエステ
ルアミドは、ポリエーテルをソフトセグメントとし、ポ
リエステルアミドあるいはポリアミドをハードセグメン
トとするブロック共重合体であり、公知の方法で製造す
ることができる。Component (C) of the composition of the present invention is at least one of polyether amide and polyether ester amide. Polyetheramide and polyetheresteramide are block copolymers having polyether as a soft segment and polyesteramide or polyamide as a hard segment, and can be produced by a known method.
ポリエステルアミド部分およびポリアミド部分であるハ
ードセグメントは、例えば炭素原子数6以上のアミノカ
ルボン酸またはラクタムもしくは炭素原子6以上のジア
ミンとカルボン酸の塩から形成される。The polyesteramide portion and the hard segment which is the polyamide portion are formed, for example, from a salt of an aminocarboxylic acid or lactam having 6 or more carbon atoms or a diamine having 6 or more carbon atoms and a carboxylic acid.
それらの例としては、例えばω−アミノカプロン酸、ω
−アミノエナント酸、ω−アミノカプリン酸、ω−アミ
ノペルゴン酸、1.1−アミノウンデカン酸および12
−アミノドデカン酸などのアミノカルボン酸あるいはカ
プロラクタム、エナントラクタム、カプリルラクタムお
よびラウロラクタムなどのラクタムおよびヘキサメチレ
ンジアミン−アジピン酸塩、ヘキサメチレンジアミン−
セバシン酸塩およびヘキサメチレンジアミン−イソフタ
ル酸塩などのジアミン−ジカルボン酸の塩があげられる
。これらのうちへキサメチレンジアミン−アジピン酸塩
が特に好ましく用いられる。Examples of these include, for example, ω-aminocaproic acid, ω
-aminoenantoic acid, ω-aminocapric acid, ω-aminopergonic acid, 1,1-aminoundecanoic acid and 12
- Aminocarboxylic acids such as aminododecanoic acid or lactams such as caprolactam, enantholactam, capryllactam and laurolactam and hexamethylene diamine - adipate, hexamethylene diamine -
Mention may be made of salts of diamine-dicarboxylic acids such as sebacate and hexamethylene diamine-isophthalate. Among these, hexamethylene diamine adipate is particularly preferably used.
ポリエーテル部分であるソフトセグメントは、例えばポ
リエチレングリコール、ポリ(1,2−プロピレンオキ
シド)グリコール、ポリ(l、3−プロピレンオキシド
)グリコール、ポリ(テトラメチレンオキシド)グリコ
ール、ポリ(ヘキサメチレンオキシド)グリコール、エ
チレンオキシドとプロピレンオキシドのブロックまたは
ランダム共重合体およびエチレンオキシドとテトラヒド
ロ7ランのブロックまたはランダム共重合体などが用い
られる。The soft segment which is a polyether moiety is, for example, polyethylene glycol, poly(1,2-propylene oxide) glycol, poly(l,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol. , a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydro-7 run.
これらの中でも帯電防止性が優れる点で特にポリエチレ
ングリコールが好ましい。Among these, polyethylene glycol is particularly preferred since it has excellent antistatic properties.
これらのポリ(アルキレンオキシド)グリコールの数平
均分子量は好ましくは200〜a o o o。The number average molecular weight of these poly(alkylene oxide) glycols is preferably 200 to aooo.
特に好ましくは250〜300oの範囲にある。Particularly preferably, the temperature is in the range of 250 to 300 degrees.
この数平均分子量において、帯電防止効果が特に優れま
た機械的性質の優れたポリエーテルアミド又はポリエー
テルエステルアミドを与える。At this number average molecular weight, a polyether amide or polyether ester amide with particularly excellent antistatic effect and excellent mechanical properties can be obtained.
ポリエーテルエステルアミドを構成するジカルボン酸成
分としては、例えば炭素原子数4〜2゜のジカルボン酸
が好ましい。その例としてはテレフタル酸、イソフタル
酸、フタル酸、ナフタレン−2,6−ジカルボン酸、ナ
フタレン−2,7−ジカルボン酸、ジフェニル−4,4
’−ジカルボン酸、ジフェノキシエタンジカルポン酸お
よび3スルホイソフタル酸ナトリウムのごとき芳香族ジ
カルボン酸、l、4−シクロヘキサンジカルボン酸、1
.2−シクロヘキサンジカルボン酸のごとき脂肪族ジカ
ルボン酸およびコハク酸、シュウ酸、アジピン酸、セバ
シン酸、およびドデカンジ酸のごとき脂肪酸ジカルボン
酸などが挙げられる。The dicarboxylic acid component constituting the polyether ester amide is preferably a dicarboxylic acid having 4 to 2 degrees of carbon atoms. Examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid.
'-dicarboxylic acids, aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, l,4-cyclohexanedicarboxylic acid, 1
.. Included are aliphatic dicarboxylic acids such as 2-cyclohexanedicarboxylic acid and fatty acid dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid.
特にテレフタル酸、イソフタル酸、l、4−シクロヘキ
サンジカルボン酸、セバシン酸およびドデカンジ酸が重
合性、色調および物性の点から好ましく用いられる。In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.
本発明の組成物は、上記(A)、(B)および(C)成
分樹脂を含有し、これらの合計量に基づいて、カルボキ
シル基含有不飽和化合物を共重合成分として含有するゴ
ム強化スチレン系共重合体樹脂[(A)成分1は22〜
45重量%であり、(B)成分であるスチレン系共重合
体樹脂は50〜77重量%であり、そして(C)成分は
1〜26重量%である。The composition of the present invention contains the above (A), (B), and (C) component resins, and based on the total amount thereof, a rubber-reinforced styrenic resin containing a carboxyl group-containing unsaturated compound as a copolymer component. Copolymer resin [(A) component 1 is 22~
The content of the styrene copolymer resin as component (B) is 50 to 77% by weight, and the content of component (C) is 1 to 26% by weight.
(A)成分が下限に至らない場合には得られる組成物の
耐衝撃性、ウェルド強度が低く、また上限を越えると、
得られる組成物の耐衝撃性、ウェルド強度、成形外観が
悪くなる。(A)成分は好ましくは22〜43重量%で
あり、更に好ましくは24〜40重量%である。If the component (A) does not reach the lower limit, the resulting composition will have low impact resistance and weld strength, and if it exceeds the upper limit,
The impact resistance, weld strength, and molded appearance of the resulting composition deteriorate. The content of component (A) is preferably 22 to 43% by weight, more preferably 24 to 40% by weight.
(B)成分が下限に至らない場合には、得られる組成物
の耐衝撃性が低く、一方上限を越えると、得られる組成
物のウェルド強度が低くなる。(B)成分は好ましくは
50〜75重量%であり、更に好ましくは55〜70重
量%である。If component (B) does not reach the lower limit, the resulting composition will have low impact resistance, while if it exceeds the upper limit, the weld strength of the resulting composition will decrease. The amount of component (B) is preferably 50 to 75% by weight, more preferably 55 to 70% by weight.
また、(C)成分が下限に至らない場合は、得られる組
成物の帯電防止効果、成形加工性が悪くなり、一方上限
を越えると得られる組成物の剛性と耐熱性が低下する。Furthermore, if the content of component (C) does not reach the lower limit, the antistatic effect and moldability of the resulting composition will deteriorate, while if it exceeds the upper limit, the rigidity and heat resistance of the resulting composition will decrease.
(C)成分は好ましくは3〜25重量%であり、更に好
ましくは5〜25重量%である。The amount of component (C) is preferably 3 to 25% by weight, more preferably 5 to 25% by weight.
本発明の組成物を製造する際の(A)、(B)、(C)
成分の混合には通常の方法が用いられる。(A), (B), (C) when producing the composition of the present invention
Conventional methods are used for mixing the ingredients.
例えば、ミキサーで各成分を混合した後、押出機にて2
00〜320°Cで溶融混練して造粒する。For example, after mixing each component with a mixer, 2
The mixture is melt-kneaded and granulated at 00 to 320°C.
さらに簡単には各成分を直接成形機内で溶融混練して成
形することができる。More simply, each component can be directly melt-kneaded and molded in a molding machine.
本発明の組成には酸化防止剤例えば2,6−ジt−ブチ
ル−4−メチルフェノール、2−(l−メチルシクロヘ
キシル)−4,6−シメチルフエノール、2.2−メチ
レン−ビス−(4−エチル−6−t−ブチルフェノール
)、トリス(ジノニルフェニル)ホスファイト;紫外線
吸収剤例えIf p −t−プチルフェニルサリシレー
ト、2゜2′−ジヒドロキシ−4−メトキシベンゾフェ
ノン、2−(2’−ヒドロキシ−4′−n−オクトキシ
フェニル)ベンゾトリアゾール;滑剤、例えばパラフィ
ンワックス、ステアリン酸、硬化油、ステアロアミド、
メチレンビスステアロアミド、n−ブチルステアレート
ケトンワックス、オクチルアルコール、ヒドロキシステ
アリン酸トリグリセリド;難燃剤例えば酸化アンチモン
、水酸化アルミニウム、はう酸亜鉛、トリクレジルホス
フェート、トリス(ジクロロプロピル)ホスフェート、
塩素化パラフィン、テトラブロモブタン、ヘキサブロモ
ベンゼン、テトラブロモビスフェノールA;帯電防止剤
例えば、ステエロアミドプロビルジメチルーβ−ヒドロ
キシエチルアンモニウムニトレート;着色剤例えば、酸
化チタン、カーボンブラック:充填剤例えば炭酸カルシ
ウム、クレー、シリカ、ガラス繊維、ガラス球、カーボ
ン繊維、顔料などを必要に応じて添加することができる
。The compositions of the present invention include antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2-(l-methylcyclohexyl)-4,6-dimethylphenol, 2,2-methylene-bis-( 4-ethyl-6-t-butylphenol), tris(dinonylphenyl)phosphite; -hydroxy-4'-n-octoxyphenyl)benzotriazole; lubricants such as paraffin wax, stearic acid, hydrogenated oils, stearamide,
Methylene bisstearamide, n-butyl stearate ketone wax, octyl alcohol, hydroxystearic triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, zinc oxalate, tricresyl phosphate, tris(dichloropropyl) phosphate,
Chlorinated paraffins, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agents such as steroamidoprobyl dimethyl-β-hydroxyethylammonium nitrate; colorants such as titanium oxide, carbon black; fillers such as Calcium carbonate, clay, silica, glass fibers, glass spheres, carbon fibers, pigments, etc. can be added as necessary.
e 実施例
次に実施例を挙げて、本発明をさらに具体的に説明する
。e. Examples Next, the present invention will be explained in more detail with reference to Examples.
製造例1(カルボキシル基含有不飽和化合物を共重合し
たゴム強化スチレン系共重合体の製造)=(1) ゴ
ム質重合体の製造方法:
4段パドル翼を備えた内容積100Qのステンレス製重
合反応器を用いて表1に示した処方にて重合反応を実施
した。パドル翼の回転数9Orpmの撹拌下に昇温し、
温度が50℃に達しj;時点で過硫酸カリウムを添加し
、以後、反応温度を50℃で一定に保つように制禦しな
がら重合反応をおこない重合率が90%に達した時点で
ジエチルヒドロキシアミン0.1重量部を添加して反応
を停止させ、水蒸気蒸留により未反応上ツマ−を実質的
に留去し、ゴム状物質のラテックスを得た。Production Example 1 (Production of rubber-reinforced styrenic copolymer copolymerized with carboxyl group-containing unsaturated compound) = (1) Production method of rubbery polymer: Stainless steel polymerization machine with internal volume of 100Q equipped with four-stage paddle blades A polymerization reaction was carried out according to the recipe shown in Table 1 using a reactor. Raise the temperature while stirring at a rotation speed of 9 Orpm with paddle blades,
When the temperature reached 50°C, potassium persulfate was added, and thereafter the polymerization reaction was carried out while controlling the reaction temperature to be kept constant at 50°C. When the polymerization rate reached 90%, diethyl hydroxyl was added. The reaction was stopped by adding 0.1 part by weight of amine, and the unreacted slag was substantially distilled off by steam distillation to obtain a rubbery latex.
表1
(2) カルボキシル基含有不飽和化合物共重合グラフ
ト共重合体の製造方法:
撹拌翼を備えた7I2ガラス製フラスコに、イオン交換
水100部、ドデシルベンゼンスルホン酸ナトリウム0
.5部、水酸化カリウム0.01部、【−ドデンルメル
力ブタン0.1部並びに表2に示す割合で表1のゴム質
重合体ラテックスと各種単量体からなるバッチ重合成分
を加え、撹拌しながら昇温しな。温度が45℃に達した
時点でエチレンジアミン四酢酸ナトリウム塩0.1部、
硫酸第1鉄0.003部、ホルムアルデヒドナトリウム
スルホキシラート・二水塩0.2部、およびイオン交換
水15部よりなる活性他剤水溶液およびジイソプロピル
ベンゼンヒドロパーオキシド0゜1部を添加し、1時間
反応をつづけた。その後、イオン交換水50部、ドデシ
ルベンゼンスルホン酸ナトリウム1部、水酸化カリウム
0.02部、t−ドデシルメルカプタン0.1部、ジイ
ソプロピルベンゼンヒドロパーオキシド0.2部および
表2に示す割合の各種単量体よりなるインクレメント重
1 ・混合物を3時間にわたって連続的に添加し反
応を続けた。添加終了後、さらに撹拌しながら1時間反
応を続けた後、2,2−メチレン−ビス−(4−エチル
−6−t−ブチルフェノール)0.2重量部を添加し、
反応生成物をフラスコより取り出した。塩化カリウム2
重量部を用いて生成物を凝固させ、脱水、水洗、乾燥を
おこなって粉末状のグラフト樹脂を回収した。表2に七
ツマー重合転化率並びに先に述べた方法で測定したグラ
フト率極限粘度[η]を示した。Table 1 (2) Method for producing carboxyl group-containing unsaturated compound copolymerized graft copolymer: In a 7I2 glass flask equipped with a stirring blade, 100 parts of ion-exchanged water and 0 parts of sodium dodecylbenzenesulfonate were added.
.. Add 5 parts of potassium hydroxide, 0.01 part of potassium hydroxide, 0.1 part of butane, and batch polymerization components consisting of the rubbery polymer latex and various monomers in Table 1 in the proportions shown in Table 2, and stir. Do not raise the temperature while doing so. When the temperature reached 45°C, 0.1 part of ethylenediaminetetraacetic acid sodium salt,
Add 0.003 parts of ferrous sulfate, 0.2 parts of formaldehyde sodium sulfoxylate dihydrate, and 15 parts of ion-exchanged water and 0.1 part of diisopropylbenzene hydroperoxide. The reaction continued for hours. Thereafter, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzene sulfonate, 0.02 part of potassium hydroxide, 0.1 part of t-dodecylmercaptan, 0.2 part of diisopropylbenzene hydroperoxide and various amounts of the proportions shown in Table 2 were added. The reaction was continued by continuously adding 1/2 increment mixture of monomers over a period of 3 hours. After the addition was completed, the reaction was continued for 1 hour while stirring, and then 0.2 parts by weight of 2,2-methylene-bis-(4-ethyl-6-t-butylphenol) was added.
The reaction product was taken out from the flask. potassium chloride 2
The product was coagulated using parts by weight, and the powdered graft resin was recovered by dehydration, washing with water, and drying. Table 2 shows the seven-mer polymerization conversion rate and the graft rate intrinsic viscosity [η] measured by the method described above.
表2 同様の方法で、 表3に示した処方で表3 (重合 体組成) の重合体を得た。Table 2 In a similar way, Table 3 with the prescription shown in Table 3 (polymerization body composition) A polymer was obtained.
(3) カルボキシル基含有化合物を含まないスチレン
系共重合体の樹脂の製造:
上記(2)に記載の方法と同様にして、表4に記載の処
方で表4に記載の重合体を得た。(3) Production of styrenic copolymer resin containing no carboxyl group-containing compound: In the same manner as described in (2) above, the polymers listed in Table 4 were obtained using the formulations listed in Table 4. .
表4
(4) 下記ポリエーテルアミドおよびポリエーテルエ
ステルアミドを準備した。Table 4 (4) The following polyether amide and polyether ester amide were prepared.
ポリエーテルアミド:カプロラクタム50部および数平
均分子量1000のポリエチレングリコール50部から
得られたものである。Polyetheramide: obtained from 50 parts of caprolactam and 50 parts of polyethylene glycol having a number average molecular weight of 1000.
ポリエーテルエステルアミド:カプロラクタム50部、
数平均分子量1000のポリエチレングリコール40部
およびアジピン酸7部から得られたものである。Polyether ester amide: 50 parts of caprolactam,
It was obtained from 40 parts of polyethylene glycol having a number average molecular weight of 1000 and 7 parts of adipic acid.
実施例1〜7、比較例1〜8
表6に示す各成分を40m/m押出機を用いて温度23
0℃で溶融混練りしてペレットを作成しjこ 。Examples 1 to 7, Comparative Examples 1 to 8 Each component shown in Table 6 was heated at a temperature of 23 cm using a 40 m/m extruder.
Create pellets by melting and kneading at 0°C.
このペレットを50z射出成形機(東芝(株)製l5−
8OA)を用いて成形温度240°Cで成形し試験片を
作成した。The pellets were molded using a 50z injection molding machine (Toshiba Corporation l5-
8OA) at a molding temperature of 240°C to create a test piece.
衝撃強度
アイゾツト衝撃強度(ASTM D256、ノツチ付
1/4#厚み)、落錘強度(厚み2.4 m/用のテス
トピースに、5kgの打撃体(径11nch)を1mよ
り落下させて、破壊エネルギーを求める)を測定した。Impact strength Izot impact strength (ASTM D256, notched 1/4 #thickness), falling weight strength (2.4 m/thickness) A 5 kg impacting body (diameter 11 nch) was dropped from 1 m onto a test piece and destroyed. (Determine the energy) was measured.
ウェルド強度
ASTMI号ダンベルの中央にウェルドラインの出る金
型を用いて成形した試験片で引張強度(Tw)を測定し
、次にウェルドラインの入らない金型で成形した試験片
を用いて引張強度(T o )を測定する。(Tw/T
o)X 100%でウェルド強度(保持率)を求めた。Weld Strength The tensile strength (Tw) was measured using a test piece molded using a mold with a weld line in the center of an ASTMI dumbbell, and then the tensile strength was measured using a test piece molded using a mold without a weld line. (T o ) is measured. (Tw/T
o) Weld strength (retention rate) was determined at X 100%.
成形外観
50z射出成形機で20cmX20cmX2゜4mmの
試験片を成形し、光沢度を測定した。Molding Appearance: A test piece measuring 20 cm x 20 cm x 2°4 mm was molded using a 50z injection molding machine, and its glossiness was measured.
表面固有抵抗性
表面抵抗計(三菱油化部、H1resta)を用いて測
定した。Surface resistivity was measured using a surface resistance meter (Mitsubishi Yukabu, H1resta).
帯電減衰率
5Latic Honestometer (S HI
S I Do Co。Charge decay rate 5Latic Honestometer (S HI
S I Do Co.
L td)を用いて試験片に8kvの電圧を1分間印加
し、そののち、電圧を取り除いて電荷量を測定し、初期
値の半分になるまでの時間を測定した。A voltage of 8 kV was applied to the test piece for 1 minute using the Ltd), and then the voltage was removed to measure the amount of charge, and the time required for it to become half of the initial value was measured.
これを半減期の値(5ec)とした。この値が小さい程
帯電防止性に優れる。This was taken as the half-life value (5 ec). The smaller this value is, the better the antistatic property is.
f9発明の効果
以上から明らかなごとく、本発明によれば帯電防止効果
に持続性があり耐衝撃性、ウェルド強度、成形外観の優
れた熱可塑性樹脂組成物を提供することができる。また
得られた熱可塑性樹脂組成物は各種の物性のバランスが
高水準にあり、最近の厳しい品質要求に対応できる優れ
た樹脂材料である。f9 Effects of the Invention As is clear from the above, the present invention can provide a thermoplastic resin composition that has a long-lasting antistatic effect and is excellent in impact resistance, weld strength, and molded appearance. Furthermore, the obtained thermoplastic resin composition has a high level of balance in various physical properties, and is an excellent resin material that can meet recent strict quality requirements.
ほか1名1 other person
Claims (1)
分として含有するゴム強化スチレン系共重合体樹脂、 (B)カルボキシル基含有不飽和化合物を共重合成分と
して含有しないゴム強化もしくは非強化スチレン系共重
合体樹脂および (C)ポリエーテルアミドおよびポリエーテルエステル
アミドの少くともいずれか一方 を含有して成り、そして (D)上記(A)、(B)および(C)成分の合計量を
基準として、(A)成分は22〜45重量%の範囲にあ
り、(B)成分は50〜77重量%の範囲にありそして
(C)成分は1〜26重量%の範囲にあり、 (E)上記(A)成分樹脂中の該カルボキシル基含有化
合物の含有量は(A)成分に基づき0.1〜10重量%
の範囲にあり且つ(A)、(B)および(C)成分の合
計量に基づき0.02〜4重量%の範囲にあり、 (F)上記(A)成分樹脂中のゴム成分又は上記(B)
成分樹脂がゴム成分を含有する場合には(A)成分樹脂
と(B)成分樹脂中のゴム成分について、平均グラフト
率が少くとも20重量%であり且つアセトン可溶分の極
限粘度(30℃、メチルエチルケトン中)が少くとも0
.35dl/gであり、そして (G)上記(A)、(B)および(C)成分の合計量を
基準としてゴム成分の含有量が5〜40重量%の範囲に
ある、 ことを特徴とする熱可塑性樹脂組成物。[Claims] 1. (A) Rubber-reinforced styrenic copolymer resin containing a carboxyl group-containing unsaturated compound as a copolymerization component; (B) Rubber not containing a carboxyl group-containing unsaturated compound as a copolymerization component. a reinforced or non-reinforced styrenic copolymer resin; (C) at least one of polyether amide and polyether ester amide; and (D) the above (A), (B) and (C). Based on the total amount of ingredients, component (A) is in the range of 22 to 45% by weight, component (B) is in the range of 50 to 77% by weight, and component (C) is in the range of 1 to 26% by weight. (E) The content of the carboxyl group-containing compound in the (A) component resin is 0.1 to 10% by weight based on the (A) component.
and in the range of 0.02 to 4% by weight based on the total amount of components (A), (B) and (C), B)
When the component resin contains a rubber component, the average grafting rate of the rubber component in the component resin (A) and the component resin (B) is at least 20% by weight, and the intrinsic viscosity of the acetone soluble portion (30°C , in methyl ethyl ketone) is at least 0
.. 35 dl/g, and (G) the content of the rubber component is in the range of 5 to 40% by weight based on the total amount of the above components (A), (B), and (C). Thermoplastic resin composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16271488A JPH0214232A (en) | 1988-07-01 | 1988-07-01 | Thermoplastic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP16271488A JPH0214232A (en) | 1988-07-01 | 1988-07-01 | Thermoplastic resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0214232A true JPH0214232A (en) | 1990-01-18 |
Family
ID=15759897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP16271488A Pending JPH0214232A (en) | 1988-07-01 | 1988-07-01 | Thermoplastic resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0214232A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0512386U (en) * | 1991-07-30 | 1993-02-19 | 川崎重工業株式会社 | Frame structure |
US6962956B2 (en) | 2002-01-31 | 2005-11-08 | Atofina | Antistatic strenique polymer compositions |
-
1988
- 1988-07-01 JP JP16271488A patent/JPH0214232A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0512386U (en) * | 1991-07-30 | 1993-02-19 | 川崎重工業株式会社 | Frame structure |
US6962956B2 (en) | 2002-01-31 | 2005-11-08 | Atofina | Antistatic strenique polymer compositions |
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